CN103803744A - Treatment method of copper-containing micro-etching waste liquid - Google Patents
Treatment method of copper-containing micro-etching waste liquid Download PDFInfo
- Publication number
- CN103803744A CN103803744A CN201410036493.4A CN201410036493A CN103803744A CN 103803744 A CN103803744 A CN 103803744A CN 201410036493 A CN201410036493 A CN 201410036493A CN 103803744 A CN103803744 A CN 103803744A
- Authority
- CN
- China
- Prior art keywords
- copper
- waste liquid
- filtrate
- complexing
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02W30/54—
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a treatment method of copper-containing micro-etching waste liquid. The method comprises the following steps: (1) reducing: adding reducing iron powder into the copper-containing micro-etching waste liquid, fully reacting, performing solid-liquid separation, collecting a filter cake, and feeding filtrate into a next procedure; (2) complexing: adding a Cu heavy metal ion collecting agent into the filtrate obtained in the step (1), complexing, depositing, performing solid-liquid separation on a solution formed after complexing, collecting a filter cake, and feeding filtrate into a next procedure; (3) performing oxidative polymerization: oxidizing ferrous sulfate in the filtrate obtained in the step (2) to produce polymeric ferric sulfate, and removing CODcr in the waste water. The copper-containing micro-etching waste liquid produced during electronic manufacturing is treated and comprehensively utilized, so that the environment is protected, resource energy is saved, and heavy metal copper and polymeric ferric sulfate serving as a water purifying agent in sewage treatment plants are provided for the development of the national economy. The treatment method is low in cost, small in investment, low in running cost, and suitable for industrial production.
Description
Technical field
The present invention relates to the treatment process of waste water, refer to particularly a kind for the treatment of process of cupric micro-etched waste liquid.
Background technology
Cupric micro-etched waste liquid extensively derives from the industries such as electronics, plating, smelting, chemical industry.Along with the development of domestic Development Techniques and the continuous input of external electronic product, electronics cupric micro-etched waste liquid needs treatment capacity to increase year by year.And people have been fully recognized that the harm that various waste discharges cause environment, various cupric micro-etched waste liquids must strictly be processed qualified discharge.
Carried out a large amount of scientific researches for the processing of cupric micro-etched waste liquid both at home and abroad, and be summed up and mainly contain following several method:
1, chemical precipitation method:
This method is applicable to the waste water of copper content below 800～1000mg/L, is to generating copper hydroxide precipitation with the PH of alkali raising waste water.This method can obtain good copper removal effect, but in precipitation, impurity separates trouble, and processing costs is higher at ordinary times.And in cupric micro-etching solution, the CODcr in waste water cannot remove, must increase other the method except CODcr.
2, substitution method:
Under acidic conditions, compared with active metal, copper is cemented out with iron filings etc.This method can reach improvement requirement, but impurity separation difficulty in precipitation, sludge quantity is many.
3, ion exchange method:
This method is applicable to the waste water of cupric concentration at 50～200mg/L.Excessive concentration, the pH value of waste water certainly will be lower, if with weakly acidic cation-exchange resin, be difficult to absorbing copper ion; If less with storng-acid cation exchange resin exchange capacity, when regeneration with more acid.With the lower waste water of resin cation (R.C.) Treatment of Copper amount, iron ion also can be by resin absorption, is difficult to separate after wash-out.Therefore, adopt this method Treatment of Copper micro-etched waste liquid cannot reach satisfied effect.
4, electrolytic process
Electrolytic process is used widely in processing copper sulfate waste water.Particularly electrolytic process-ion exchange method combination, or use the combination of electrolytic process-chemical precipitation method.
Generally adopt electrolytic process to reclaim copper for the copper in micro-etching solution in printed circuit board, traditional electrolysis reactor is mostly rectangular box type electrolyzer.This electrolyzer electroprecipitation speed is slow, is subject to the restriction of low copper concentration.Electrolysis in low concentration solution, the form of gained copper is bad, affects its commercial value.Wang is take tubulose EMEW cell as electrochemical reactor, reclaim the copper in micro-etched waste liquid, anode used is the titanium electrode that applies platinum metals, negative electrode is cylindric stainless steel, control current density is ZA/dm2, cathode efficiency is more than 90%, and copper purity is 97%, but this electrolytic process is just difficult to separate out to the concentration copper of 8g/L again.
Remove in the waste water after copper and mostly contain ferrous sulfate, CODcr, in technique, the general catalytic oxidation that adopts is produced bodied ferric sulfate.Although this method is simple, catalyst n aNO
2be carcinogenic substance, and in production process, dosage is large, the nitrite ion in product easily exceeds standard, and has limited its application in drinking water treatment; Nitrogen oxide is discharged, contaminate environment, postprocessing working procedures complexity; Speed of response is slow, adapt to large-scale industrial production, needs to adopt innovative approach.
Summary of the invention
Object of the present invention will overcome exactly prior art and adopt the existing deficiency of substitution method Treatment of Copper micro-etched waste liquid, and a kind for the treatment of process of cupric micro-etched waste liquid with low cost is provided.
For achieving the above object, the treatment process of cupric micro-etched waste liquid of the present invention, comprises the following steps:
1) reduction: in cupric micro-etched waste liquid, add reduced iron powder, after abundant reaction, carry out solid-liquid separation with plate-and-frame filter press, collection filter cake, filtrate is carried out lower step operation;
2) complexing: add Cu heavy metal capturing agent to carry out complexing postprecipitation in the filtrate of step 1) gained, the solution after complexing completes carries out solid-liquid separation with plate-and-frame filter press again, collects filter cake, and filtrate is carried out lower step operation;
3) oxypolymerization: step 2) ferrous sulfate in gained filtrate produces bodied ferric sulfate through oxidation, and removes the CODcr in waste water simultaneously.
In step 1) of the present invention, purity >=98% of reduced iron powder.Step 2) in, the active group of described Cu heavy metal capturing agent is nabam.
In step 3) of the present invention, adopt hydrogen peroxide oxidation method or sodium chlorate oxidation style that ferrous sulfate is oxidized.Preferably sodium chlorate oxidation style, because adopting the production technique of sodium chlorate oxidation style simple, facility investment is few, and product stability is good, and reaction efficiency is high, without atmospheric pollution; In product, contain oxymuriate, can double as coagulation and sterilant.
Step 1) of the present invention and step 2) in, the filter cake of collecting gained is copper sponge.Copper sponge can be sold to smeltery's copper smelting, and waste recycling economizes on resources.
The present invention first adopts substitution method that the copper of cupric micro-etched waste liquid is cemented out, and by controlling the add-on of iron powder, can obtain the copper sponge of copper content more than 80%; For the incomplete trace copper of displacement, add Cu heavy metal capturing agent precipitation, can guarantee that in waste liquid, total copper content is less than 0.5mg/L; Waste water after copper is removed totally adopts oxidative polymerization to produce bodied ferric sulfate, and removes the CODcr in waste water simultaneously.
Beneficial effect of the present invention is: adopt new technology the cupric micro-etched waste liquid producing in electronics manufacture is processed and fully utilized; protect environment; saved energy resource, for the development of national economy heavy metal copper is provided and for sewage work as water purification agent bodied ferric sulfate.Treatment process of the present invention with low cost, less investment, working cost is low, is applicable to suitability for industrialized production.
Embodiment
In order to explain better the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but they do not form restriction to the present invention.
Embodiment
Cupric micro-etched waste liquid derives from the micro-etching solution of certain electronics corporation, 20,000 tons of year waste liquid total amounts, and in waste liquid, main component is the about 8000mg/L of Cu, pH value is about the about 4000mg/L of 1, CODcr, and cupric ion is with hydrated ion ［ Cu (H
2o)
4?
2+exist.
The treatment process of cupric micro-etched waste liquid, comprises the following steps:
1) reduction: adding purity in 20,000 tons of cupric micro-etched waste liquids is 232.4 tons of 99% reduced iron powders, after abundant reaction, carries out solid-liquid separation with plate-and-frame filter press, 196 tons of collection copper sponges, and filtrate is carried out lower step operation;
2) complexing: add 0.8 ton of Cu heavy metal capturing agent to carry out complexing postprecipitation in the filtrate of step 1) gained, the active group of Cu heavy metal capturing agent is nabam, solution after complexing completes carries out solid-liquid separation with plate-and-frame filter press again, collect 4 tons of copper sponges, filtrate is carried out lower step operation;
3) oxypolymerization: step 2) gained filtrate employing sodium chlorate oxidation style, first add 114.82 tons, sulfuric acid, at normal temperatures, in stirring, add 1077 tons of sodium chlorate, check ferrous ion reduces to normality can be finished,
FeSO
4+NaClO
3+H
2SO
4→［Fe
2(OH)
n(SO
4)
3-n/2］+H
2O+KCl
Ferrous sulfate is through manufacture a finished product 29685.62 tons of polymeric ferrous sulphate solutions of oxidation, and removes the CODcr in waste water simultaneously.
The bodied ferric sulfate quality product that adopts the present invention to produce reaches II class in GB14591-2006: process water, black water quality standard.
Claims (5)
1. a treatment process for cupric micro-etched waste liquid, is characterized in that, comprises the following steps:
1) reduction: in cupric micro-etched waste liquid, add reduced iron powder, after abundant reaction, carry out solid-liquid separation with plate-and-frame filter press, collection filter cake, filtrate is carried out lower step operation;
2) complexing: add Cu heavy metal capturing agent to carry out complexing postprecipitation in the filtrate of step 1) gained, the solution after complexing completes carries out solid-liquid separation with plate-and-frame filter press again, collects filter cake, and filtrate is carried out lower step operation;
3) oxypolymerization: step 2) ferrous sulfate in gained filtrate produces bodied ferric sulfate through oxidation, and removes the CODcr in waste water simultaneously.
2. the method for utilizing the cupric micro-etching solution of circuit board etching to produce copper sulfate according to claim 1, is characterized in that: in step 1), and purity >=98% of reduced iron powder.
3. the method for utilizing the cupric micro-etching solution of circuit board etching to produce copper sulfate according to claim 1, is characterized in that: step 2) in, the active group of described Cu heavy metal capturing agent is nabam.
4. the method for utilizing the cupric micro-etching solution of circuit board etching to produce copper sulfate according to claim 1, is characterized in that: in step 3), adopt hydrogen peroxide oxidation method or sodium chlorate oxidation style that ferrous sulfate is oxidized.
5. the method for utilizing the cupric micro-etching solution of circuit board etching to produce copper sulfate according to claim 1, is characterized in that: step 1) and step 2) in, the filter cake of collecting gained is copper sponge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410036493.4A CN103803744B (en) | 2014-01-26 | 2014-01-26 | The treatment process of cupric micro-etched waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410036493.4A CN103803744B (en) | 2014-01-26 | 2014-01-26 | The treatment process of cupric micro-etched waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103803744A true CN103803744A (en) | 2014-05-21 |
| CN103803744B CN103803744B (en) | 2015-12-30 |
Family
ID=50701195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410036493.4A Expired - Fee Related CN103803744B (en) | 2014-01-26 | 2014-01-26 | The treatment process of cupric micro-etched waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103803744B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776312A (en) * | 2016-02-25 | 2016-07-20 | 渤海大学 | Recovery method for invalid alkaline copper-containing etching liquid |
| CN106745933A (en) * | 2015-11-23 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of ferriferous oxide produces the processing method of waste water |
| CN106800340A (en) * | 2015-11-25 | 2017-06-06 | 衡阳屹顺化工有限公司 | A kind of copper sulphate produces the processing method of waste water |
| CN110255774A (en) * | 2019-07-05 | 2019-09-20 | 金隆铜业有限公司 | The processing system and treatment process of cupric high ammonia-nitrogen wastewater |
| CN112415129A (en) * | 2020-10-26 | 2021-02-26 | 广东韶钢松山股份有限公司 | Method for detecting calcium and magnesium in sintered ore |
| CN116924544A (en) * | 2023-09-14 | 2023-10-24 | 中南大学 | Resource treatment method for microetching copper-containing wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
-
2014
- 2014-01-26 CN CN201410036493.4A patent/CN103803744B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
Non-Patent Citations (2)
| Title |
|---|
| 令玉林等: "一种多DTC基团重金属螯合剂的合成及处理含铜废水性能", 《环境工程学报》, vol. 5, no. 6, 30 June 2011 (2011-06-30), pages 1246 - 1250 * |
| 郭晓滨等: "重金属螯合剂在含铜废水处理中的应用", 《西安科技学院学报》, vol. 23, no. 4, 31 December 2003 (2003-12-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745933A (en) * | 2015-11-23 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of ferriferous oxide produces the processing method of waste water |
| CN106800340A (en) * | 2015-11-25 | 2017-06-06 | 衡阳屹顺化工有限公司 | A kind of copper sulphate produces the processing method of waste water |
| CN105776312A (en) * | 2016-02-25 | 2016-07-20 | 渤海大学 | Recovery method for invalid alkaline copper-containing etching liquid |
| CN110255774A (en) * | 2019-07-05 | 2019-09-20 | 金隆铜业有限公司 | The processing system and treatment process of cupric high ammonia-nitrogen wastewater |
| CN112415129A (en) * | 2020-10-26 | 2021-02-26 | 广东韶钢松山股份有限公司 | Method for detecting calcium and magnesium in sintered ore |
| CN116924544A (en) * | 2023-09-14 | 2023-10-24 | 中南大学 | Resource treatment method for microetching copper-containing wastewater |
| CN116924544B (en) * | 2023-09-14 | 2023-12-19 | 中南大学 | Resource treatment method for microetching copper-containing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103803744B (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803744B (en) | The treatment process of cupric micro-etched waste liquid | |
| CN101391800B (en) | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid | |
| CN101658941B (en) | Technology for extracting copper powder from waste materials generated in circuit board manufacturing plants by compound extraction method | |
| CN105858987B (en) | The recycling treatment process of pure water pure nickel is reclaimed from electronickelling poaching wastewater | |
| CN102071319B (en) | Method for preparing high-purity silver from silver-containing waste liquid | |
| CN111560615B (en) | Method for on-line recovery of copper and chlorine from acidic etching waste liquid and regeneration of etching liquid | |
| CN102303917B (en) | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards | |
| CN103936081A (en) | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| CN105385851A (en) | Treatment method of acid pickling waste liquid | |
| CN113526621B (en) | Method and device for treating nitrate-containing waste liquid | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN110759532A (en) | High-salt concentrated water treatment process for producing iron phosphate by sodium method | |
| WO2016029613A1 (en) | Method and apparatus for purifying desulfurization lead plaster filtrate | |
| CN112708885A (en) | Recycling method and system for copper-etching waste nitric acid | |
| CN101372746A (en) | Copper resource cyclic regeneration method in manufacture process | |
| CN103397341B (en) | A kind of method reclaiming copper from alkaline spent etching solution | |
| CN113481541B (en) | Method for recovering manganese metal by using electrolytic manganese slag leachate | |
| CN108505043B (en) | Method for regenerating and recycling PCB (printed Circuit Board) acidic etching waste liquid | |
| CN102191378A (en) | Electrolyte preparation process for electrolyzing manganese | |
| CN109809652A (en) | A kind of chemical nickel Wastewater by Electric treatment by catalytic oxidation and system | |
| CN102925899A (en) | Method for refining copper chloride etching waste liquor | |
| CN102070436A (en) | Method for recovering oxalate and acid liquor from acidic etching waste liquor | |
| CN112813268A (en) | PCB (printed circuit board) copper electroplating and acid etching copper resource recycling method | |
| CN107313069A (en) | A kind of method by acid, the mashed up recovery copper of alkali spent etching solution | |
| CN110790427A (en) | Treatment and recovery process of alkaline etching wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151230 Termination date: 20190126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |